NMR-microscopy with TrueFISP at 11.75T

The purpose of this paper is to demonstrate that a fully balanced gradient echo technique (TrueFISP) can be used for microscopic experiments at high static magnetic field strengths. TrueFISP experiments were successfully performed on homogeneous and inhomogeneous objects at 11.75T. High-resolution TrueFISP images were obtained from phantoms, plants, formalin-fixed samples, and from an isolated beating rat heart with an in-plane resolution of 78 micro m and a slice thickness of 500 micro m. The signal-to-noise ratio (SNR) gain of TrueFISP compared to conventional gradient echo or spin echo sequences will allow faster acquisition times or an improvement in spatial resolution for microscopic experiments.     

The Ground State Energy of a Dilute Two-Dimensional Bose Gas

The ground state energy per particle of a dilute, homogeneous, two-dimensional Bose gas, in the thermodynamic limit is shown rigorously to be E₀/N=(2²/m)|ln(a²)|^–1, to leading order, with a relative error at most O(|ln(a²)|^–1/5). Here N is the number of particles, =N/V is the particle density and a is the scattering length of the two-body potential. We assume that the two-body potential is short range and nonnegative. The amusing feature of this result is that, in contrast to the three-dimensional case, the energy, E₀ is not simply N(N–1)/2 times the energy of two particles in a large box of volume (area, really) V. It is much larger.     

Stringent tests of shell model calculations in fp shell nuclei (46, 48)Ti and (50,52)Cr from measurements of g factors and B(E2) values

Measurements of magnetic moments and lifetimes of 2(+)(1) and 4(+)(1) states of (46,48)Ti and (50,52)Cr were performed with high accuracy via projectile Coulomb excitation and the technique of transient magnetic fields. The high quality of the data allows for the first time to establish stringent constraints on large scale shell model calculations. Whereas the global behavior of the data is well explained by full fp shell model calculations, distinct deviations in the g factors and B(E2) values of (46,48)Ti from theoretical predictions can be attributed to excitations of the 40Ca core. This suggestion is supported by recent Monte Carlo calculations which provide evidence that 48Ca is a better inert core.     

CO adsorption on epitaxially grown Pt layers on Ru(0 0 0 1)

The adsorption of CO on epitaxially grown Pt films of variable thickness has been studied using infrared-absorption spectroscopy, scanning tunnelling microscopy and thermal desorption spectroscopy. Depending on the number of pseudomorphic Pt layers (N_Pt = 1-4) the internal and external CO stretching modes (ν_C-O and ν_Pt-CO, respectively) display characteristic frequency shifts due to the vanishing influence of the underlying Ru(0 0 0 1) substrate and Pt/Ru interface. For thicker layers (N_Pt ? 5) when this influence has become negligible, the compressive stress within the Pt film is gradually relieved, leading to a dislocation network. The structural heterogeneity during the ongoing relaxation process of the Pt film is reflected in the ν_C-O line shape; no line broadening is observed for either pseudomorphic or very thick films (N_Pt ? 15). For N_Pt ? 3 the adsorption of CO on Pt/Ru(0 0 0 1) films closely resembles CO on Pt(1 1 1), with residual deviations in line position and desorption temperatures gradually converging to zero.     

The Photoenolization of 2-Methylacetophenone and Related Compounds

A reinvestigation of 2-methylacetophenone ( 1 ) by ns flash photolysis has provided detailed evidence for the reaction sequence of photoenolization. The triplet reaction proceeds adiabatically from the lowest excited triplet state of the ketone, ³ K (1) , to the enol excited triplet state, ³ E (1) , which decays both to enol and ketone ground state. The Z- and E-isomers of the photoenol, Z- E (1) and E- E (1) are formed in about equal yield by the triplet pathway, while direct enolization from the lowest excited singlet state of 1 yields (predominantly) the Z-isomer. Intramolecular reketonization from Z- E (1) to 1 proceeds at a rate of ca. 10⁸s^?1 in cyclohexane, but can be retarded to ca. 10⁴s^?1 in hydrogen-bond-acceptor solvents. The proposed mechanism is summarized in Scheme 1 and rationalized on the basis of a state correlation diagram, Scheme 2. 3,3,6,8-Tetramethyl-1-tetralone ( 2 ) was used as a reference compound with fixed conformational position of the carbonyl group, and some results from a brief investigation of 2,4-dimethylbenzophenone ( 3 ) are also reported.     

Homoconjugated ketones with extended unsaturation: Wavelength-selective,regioselective, diastereoselective,and enantiospecific photochemical transformations of methyl 7-oxospiro[5.5]undeca-1,3-and -2,4,-diene-2-carboxylate

The title molecules were shown to photorearrange with remarkable selectivity. Wavelength variation steers the rearrangement modes, of which the [1,2]-acyl shift was found to be largely regioselective, diastereoselective, and enantiospecific. Chemical intercorrelation of products and mechanistic studies were carried out all along. The potential significance of these photochemical processes in selective synthetic schemes is discussed.     

CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation

Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained.     

Total synthesis of (+/-)-mersicarpine

The first total synthesis of the indole alkaloid mersicarpine is reported. Key steps include a beta-dicarbonyl radical cyclization, as well as an oxidation of the benzopyrrole moiety to establish the masked 1,2-dicarbonyl functionality. An X-ray crystal structure and discussion of the 1H NMR behavior of the natural product are also presented.     

Synthesis of β-Ketoiminato Copper(II) Complexes and Their Use in Copper Deposition

The template synthesis of ethylenediamine ( 1 ) with 2-acetylcyclopentanone ( 2 ) and [Cu(OAc)₂ · H₂O] ( 5 ) produced [Cu(1-(2-cC₅H₆(O))C(Me)NCH₂)₂)] ( 6 ) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine ( 7 , = L H)^[1] gave [Cu(μ-OAc)( L )(H₂O)]₂ ( 8 ). The solid-state structures of 6 and 8 were determined confirming that 8 possesses intra- and intermolecular hydrogen bonds resulting in a dimer formation. The thermal behavior of 6 – 8 was studied by TG and TG-MS. Under oxygen CuO was formed, whereas under Ar Cu/Cu₂O ( 6 ) or Cu ( 8 ) was obtained. Complex 6 was used as CVD precursor for Cu and Cu-oxide deposition (substrate temp., 400–500 °C, N₂, 60 mL · min^–1; O₂, 60 mL · min^–1; pressure, 0.87–1.5 mbar). The as-obtained deposits show separated particles of different appearance at the substrate surface as evidenced by SEM. Non-volatile 8 was applied as spin-coating precursor for Cu and CuO formation [conc. 0.25 mol · L^–1; volume 0.2 mL; 3000 rpm; depos. time 2 min; heating rate 50 K · min^–1; holding time 60 min (Ar), 120 min (air) at 800 °C]. The samples on silicon consist of granulated particles (Ar) or are non-dense with a grainy topography (air). EDX and XPS measurements confirmed the formation of Cu (Ar) or CuO (O₂) with up to 13 mol-% C impurity.